A series of ferrocenyl and thienyl mono- and biscarbene chromium(0) complexes 1–6 were synthesised. The complexes were characterised both spectroscopically and electrochemically, and the single crystal X-ray structure of 3 was determined. Electrochemical measurements in CH₂Cl₂ revealed that the carbene double bond of 1–6 is reduced to an anion radical, ⁻Cr–C˙ at formal reduction potentials <−1.7 V vs. FcH/FcH⁺. A computational study on 1, 3 and 4 (B3LYP/def2-SVP level) is consistent with electrochemical results in showing that electrochemically generated chromium(I) species may be further electrochemically irreversibly oxidised to chromium(II) at E_pa > 0.95 V. The reactivity towards follow-up chemical reactions of the anodically produced Cr(II) species is much higher than the reactivity of the cathodically produced radical anions as the latter was still observably reoxidised to the parent CrC species at fast scan rates. The ferrocenyl group is oxidised electrochemically reversibly to ferrocenium at larger potentials than the electrochemically reversible oxidation of the Cr(0) centre to Cr(I). That all redox centres in 1–6 are involved in one-electron transfer steps was confirmed by comparing the ferrocenyl voltammetric wave with those of the other redox centres in linear sweep voltammetric experiments. The ferrocenyl group was electrochemically shown to stabilise the CrC centre almost as much as the NHBu, and much more than the ethoxy and thienyl groups.